CN106117261A - A kind of eight hexamethylene alkylene oxide cage-type silsesquioxanes and preparation method thereof - Google Patents
A kind of eight hexamethylene alkylene oxide cage-type silsesquioxanes and preparation method thereof Download PDFInfo
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- CN106117261A CN106117261A CN201610440571.6A CN201610440571A CN106117261A CN 106117261 A CN106117261 A CN 106117261A CN 201610440571 A CN201610440571 A CN 201610440571A CN 106117261 A CN106117261 A CN 106117261A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- -1 dimethylsilyl Chemical group 0.000 claims abstract description 30
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000003756 stirring Methods 0.000 claims description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 claims description 5
- 235000014443 Pyrus communis Nutrition 0.000 claims description 4
- 239000003610 charcoal Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 229940058401 polytetrafluoroethylene Drugs 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 18
- 229920005989 resin Polymers 0.000 abstract description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 229910052710 silicon Inorganic materials 0.000 abstract description 6
- 239000010703 silicon Substances 0.000 abstract description 6
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 4
- 238000009833 condensation Methods 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 2
- 238000006459 hydrosilylation reaction Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005050 vinyl trichlorosilane Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 24
- 239000000463 material Substances 0.000 description 18
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 14
- 239000000805 composite resin Substances 0.000 description 14
- 238000002444 silanisation Methods 0.000 description 14
- 239000000377 silicon dioxide Substances 0.000 description 13
- 239000011159 matrix material Substances 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 9
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical compound C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 description 9
- 229930006711 bornane-2,3-dione Natural products 0.000 description 9
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 5
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 229910002808 Si–O–Si Inorganic materials 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 4
- KJSGODDTWRXQRH-UHFFFAOYSA-N 2-(dimethylamino)ethyl benzoate Chemical compound CN(C)CCOC(=O)C1=CC=CC=C1 KJSGODDTWRXQRH-UHFFFAOYSA-N 0.000 description 4
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 4
- 241000790917 Dioxys <bee> Species 0.000 description 4
- 229910003978 SiClx Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 235000009508 confectionery Nutrition 0.000 description 4
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 4
- 150000002496 iodine Chemical class 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000009849 vacuum degassing Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 235000002597 Solanum melongena Nutrition 0.000 description 2
- 244000061458 Solanum melongena Species 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000002769 thiazolinyl group Chemical group 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- YRCUYAQBRRTNTF-UHFFFAOYSA-N CC1OCC(CC[Si+](C)(C)OC)CC1 Chemical compound CC1OCC(CC[Si+](C)(C)OC)CC1 YRCUYAQBRRTNTF-UHFFFAOYSA-N 0.000 description 1
- BCWMBWSIQNQIHR-UHFFFAOYSA-N CCC1CC2OC2CC1 Chemical compound CCC1CC2OC2CC1 BCWMBWSIQNQIHR-UHFFFAOYSA-N 0.000 description 1
- HAEDJBHOPDKZSV-NBXIYJJMSA-N C[SiH2]CC[C@@H]1C[C@@H]2OC2CC1 Chemical compound C[SiH2]CC[C@@H]1C[C@@H]2OC2CC1 HAEDJBHOPDKZSV-NBXIYJJMSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000012656 cationic ring opening polymerization Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RCNRJBWHLARWRP-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane;platinum Chemical compound [Pt].C=C[Si](C)(C)O[Si](C)(C)C=C RCNRJBWHLARWRP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 230000009916 joint effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 125000005401 siloxanyl group Chemical group 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
Abstract
A kind of eight hexamethylene alkylene oxide cage-type silsesquioxanes and preparation method thereof relate to the preparation method of a kind of cage-type silsesquioxane.With the most industrialized tetraethyl orthosilicate base ester and Tetramethylammonium hydroxide as primary raw materials, first through synthesizing eight poly-tetramethyl ammonium cage-type silsesquioxanes, eight poly-hydrogen-based dimethylsilyl cage-type silsesquioxanes are prepared by silicon hydrogenation, eight hexamethylene alkylene oxide cage-type silsesquioxanes are prepared through hydrosilylation, compared to vinyl trichlorosilane for raw material through hydrolytic condensation, the cage-type silsesquioxane mostly being mix products of the most oxidized preparation, product structure of the present invention is single, productivity is high, simple, and the eight hexamethylene alkylene oxide cage-type silsesquioxanes prepared can be used for modified resin, prepare high performance composite.
Description
Technical field
The present invention relates to a kind of eight hexamethylene alkylene oxide cage-type silsesquioxanes and preparation method thereof.
Background technology
Hybrid inorganic-organic materials due to have excellence mechanical property, thermal property, electric property, optical property and
Cause the extensive concern of people.Polyhedral oligomeric silsesquioxane (POSS), is a kind of polymerization received significant attention in recent years
Thing is material modified, it is considered that, POSS has classical molecular structural formula (RSiQ1.5)n[n >=4], its R substituent can be hydrogen,
Alkyl, thiazolinyl, aryl, arlydene and their derivatives group；Its structure mainly has randomly, ladder type, cage modle, part cage modle
With bridge type etc.；N is generally 6,8,10,12 etc., wherein most commonly seen with n=8, is a typical polyhedral oligomeric silsesquioxane
Alkane, has the cube cage modle skeleton of high degree of symmetry.
Polyhedral oligomeric silsesquioxane (POSS) comprises inorganic and organic two parts, and inside is silicon and the inorganic knot of oxygen composition
Structure center, periphery is many to be covered by organic group, is the nano material truly with hybrid inorganic-organic structure.Its
Inorganic silicon-oxygen core cagelike structure, has good mechanical performance；Peripheral organic group has high designability with anti-
Ying Xing, can meet one or more organic active functional group.These organic substituents group can be divided into two big classes: a class is inertia base
Group, such as cyclohexyl, cyclopenta, ethyl, isobutyl group etc.；Another kind of is active group, such as all kinds of thiazolinyls, epoxy radicals, amino etc..
When POSS introduces in polymeric matrix, it is compatible that peripheral non-reacted organic group can strengthen between itself and polymeric matrix
Property；Peripheral reactive group can become covalent bond to be connected by polymerization, grafting, surface bond or other modes with occurring matrix type, real
Existing POSS is dispersed and becomes the three-dimensional novel organic-inorganic composite of molecular level, superior performance with occurring matrix type, makes material
Performance is greatly improved, and has boundless answering in fields such as space flight, aviation, electronics, optics, medicine, material high-tech
Use prospect.
At present, the synthesis of POSS mainly has following three kinds of methods: first hydrolytic condensation method, is that to prepare POSS the most direct
A kind of method, this method is with RSiX3Type monomer is raw material, and polycondensation reaction is self-assembled into corresponding POSS monomer under given conditions,
Reaction yield, by the joint effect of R, solvent and catalyst, is divided into the most again acid catalysis and two kinds of response types of base catalysis；They are two years old
Unfilled corner closed loop method, i.e. RSiX3When the most not exclusively hydrolyzing, polycondensation can generate the more stable poly-POSS of unfilled corner seven,
Obtain with water for catalyst hydrolytie polycondensation closed loop in solvent by the siloxanyl monomers waiting thing mass ratio to add containing active group again
To corresponding POSS monomer, this type of seven poly-unfilled corner POSS also can be degraded by the poly-POSS of cage type eight open loop under base catalyst effect
Arrive, by using novel alkaline catalyst, ultrapure POSS monomer can be obtained；It three is functional group's derivatization method, i.e. utilizes several
Common POSS is raw material, can be obtained the POSS derivant of a series of band active group by chemical reaction, and application is more at present
Mainly have hydrogen-based POSS and tetramethylphosphonihydroxide hydroxide ammonium POSS, the former mainly utilizes hydrogen-based and unsaturated compound to carry out silicon hydrogen to add
Becoming reaction, the latter mainly utilizes Silanization reaction to introduce new active group.The present invention i.e. elaborates and utilizes functional group to derive
Method prepares the preparation method of a kind of eight hexamethylene alkylene oxide cage-type silsesquioxanes.
Summary of the invention
The invention provides a kind of eight hexamethylene alkylene oxide cage-type silsesquioxanes and preparation method thereof, with the most industrialized
Tetraethyl orthosilicate base ester and Tetramethylammonium hydroxide are primary raw materials, first through synthesizing eight poly-tetramethyl ammonium cage modles times
Half siloxanes, prepares eight poly-hydrogen-based dimethylsilyl cage-type silsesquioxanes by silicon hydrogenation, through hydrosilylation
Prepare eight hexamethylene alkylene oxide cage-type silsesquioxanes, compared to vinyl trichlorosilane for raw material through hydrolytic condensation, then warp
The cage-type silsesquioxane mostly being mix products of oxidation preparation, product structure of the present invention is single, and productivity is high, simple.
A kind of eight hexamethylene alkylene oxide cage-type silsesquioxanes, its structural formula is as follows:
The preparation method of above-mentioned eight hexamethylene alkylene oxide cage-type silsesquioxanes, including eight poly-tetramethyl ammonium cage model sesquialter silicon
The synthesis of oxygen alkane, the preparation of eight poly-hydrogen-based dimethylsilyl cage-type silsesquioxanes, eight hexamethylene alkylene oxide cage model sesquialter silicon
Three steps of the preparation of oxygen alkane, specific as follows:
(1) in round-bottomed flask, add Tetramethylammonium hydroxide (TMAH), methanol aqueous solution, stir in ice bath, then
Add tetraethoxysilane (TEOS), be stirred at room temperature 24h, i.e. obtain the eight poly-tetramethyl ammonium cage modles being scattered in solution
Silsesquioxane；
(2) by this mixture under condition of ice bath, it is added dropwise to another and has added normal hexane and dimethylchlorosilane
(DMCS), in there-necked flask, this mixture is stirred at room temperature 3h；Use pear funnel separatory, take supernatant liquid rotation and steam, sucking filtration,
Clean 3 times with methanol, obtain white powder solid, be dried, i.e. obtain eight poly-hydrogen-based dimethylsilyl cage-type silsesquioxanes；
(3) in there-necked flask, add dry toluene, take eight poly-hydrogen-based dimethylsilyl cage-type silsesquioxanes, stirring
5min, addition 1,2-epoxy 4-vinyl cyclohexane, add platinum (0)-1,3-divinyl-1,1,3,3-tetramethyl disiloxane
Complex Pt (dvs).Stir at 50 DEG C, react 24h；Cooling, adds dry active charcoal, after stirring 5min；Mixture passes through
The poly tetrafluoroethylene of 0.45 μm, filters, vacuum rotary steam, obtains opaque viscous liquid, is eight hexamethylene alkylene oxide cage modles times
Half siloxanes.
The synthetic route of the preparation method of the present invention eight hexamethylene alkylene oxide cage-type silsesquioxane is as follows:
Synthesized by the present invention eight hexamethylene alkylene oxide cage-type silsesquioxanes can under the effect of cationic initiator
Cationic ring-opening polymerization occurs, and in course of reaction, polymerization shrinkage is less, and can introduce network cross-linked point, can be applicable to gear division
The modification of resin, improves material polymerization shrinkage and mechanical performance.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, it is exemplified below example and the present invention is entered
Row further describes in detail.It will be appreciated by those skilled in the art that described example is used only for help and understands the present invention, and
It is not used in the restriction present invention.
Embodiment 1:
The synthesis of (1) eight poly-tetramethyl ammonium cage-type silsesquioxane
The Tetramethylammonium hydroxide (TMAH) of 41.0mL is added in 500mL round-bottomed flask, 50.96mL methanol, 15mL water,
Ice bath stirs, is subsequently adding 22mL tetraethoxysilane (TEOS), under room temperature, stir 24h；Will reaction by rotary evaporator
Liquid is concentrated into 8 times, is placed in freezing in refrigerator and makes it crystallize, and crystal is washed through acetone, is vacuum dried to obtain eight poly-tetramethyl ammonium cage modles times
Half siloxanes, productivity 97%.Its nuclear magnetic resonance, NMR and infrared absorption analysis characterize data:29Si-NMR (119MHz, CD3OD,
300K, ppm)-99.1；13C-NMR (159MHz, CD3OD, 300K, ppm) 15.10；1H-NMR (600MHz, CD3OD, 300K,
ppm)3.19；FTIR(cm-1, KBr) and 3393,1643 (νN-O), 1489 (νasC-N), 1116 (νSi-O-Si)
The preparation of (2) eight poly-hydrogen-based dimethylsilyl cage-type silsesquioxanes
Take 2.85g eight poly-tetramethyl ammonium cage-type silsesquioxane, add in the there-necked flask of another 1L and (add in bottle
500mL normal hexane and 60mL dimethylchlorosilane), this mixture is stirred at room temperature 3h；Use pear funnel separatory, take upper liquid
Body rotation is steamed, and sucking filtration cleans 3 times with methanol, obtains white powder solid, is dried, i.e. obtains dimethylsilyl cage model sesquialter silica
Alkane, productivity 95%.Its nuclear magnetic resonance, NMR and infrared absorption analysis characterize data:29Si-NMR (119MHz, CD3OD, 300K,
Ppm)-108.66,1.40；FTIR(cm-1, KBr) and 2968 (νasC-H), 2147 (νSi-H), 1101 (νSi-O-Si)
The preparation of (3) eight hexamethylene alkylene oxide cage-type silsesquioxanes
20mL dry toluene, 2.0g dimethylsilyl cage-type silsesquioxane, stirring is added in 100mL there-necked flask
5min, adds 2g1,2-epoxy 4-vinyl cyclohexane, adds 0.1g platinum (0)-1,3-divinyl-1,1,3,3-tetramethyl two
Silicone complex Pt (dvs).Stir at 50 DEG C, react 24h；Cooling, adds dry active charcoal, after stirring 5min；Mixture
By the poly tetrafluoroethylene of 0.45 μm, being filled in 100mL eggplant type bottle, rotation is steamed, except solvent obtains opaque viscous liquid,
It is eight hexamethylene alkylene oxide cage-type silsesquioxanes.Its nuclear magnetic resonance, NMR and infrared absorption analysis characterize data:29Si-NMR
(119MHz, CD3OD, 300K, ppm)-108.5；FTIR(cm-1, KBr) and 2967 (νasC-H), 2145 (νSi-H), 1097 (νSi-O-Si)
Embodiment 2:
The synthesis of (1) eight poly-tetramethyl ammonium cage-type silsesquioxane
The Tetramethylammonium hydroxide (TMAH) of 41.0mL is added in 500mL round-bottomed flask, 50.96mL methanol, 15mL water,
Ice bath stirs, is subsequently adding 22mL tetraethoxysilane (TEOS), under room temperature, stir 24h；Now eight poly-tetramethyl ammonium cage
Type silsesquioxane is dispersed in reactant liquor.
The preparation of (2) eight poly-hydrogen-based dimethylsilyl cage-type silsesquioxanes
It is added drop-wise to first step reaction mixture in the there-necked flask of another 1L under condition of ice bath (add in bottle
500mL normal hexane and 60mL dimethylchlorosilane), this mixture is stirred at room temperature 3h；Use pear funnel separatory, take upper liquid
Body rotation is steamed, and sucking filtration cleans 3 times with methanol, obtains white powder solid, is dried, i.e. obtains dimethylsilyl cage model sesquialter silica
Alkane, productivity 95%.Its nuclear magnetic resonance, NMR and infrared absorption analysis characterize data:29Si-NMR (119MHz, CD3OD, 300K,
Ppm)-108.66,1.40；FTIR(cm-1, KBr) and 2968 (νasC-H), 2147 (νSi-H), 1101 (νSi-O-Si)
The preparation of (3) eight hexamethylene alkylene oxide cage-type silsesquioxanes
20mL dry toluene, 2.0g dimethylsilyl cage-type silsesquioxane, stirring is added in 100mL there-necked flask
5min, adds 2g1,2-epoxy 4-vinyl cyclohexane, adds 0.1g platinum (0)-1,3-divinyl-1,1,3,3-tetramethyl two
Silicone complex Pt (dvs).Stir at 50 DEG C, react 24h；Cooling, adds dry active charcoal, after stirring 5min；Mixture
By the poly tetrafluoroethylene of 0.45 μm, being filled in 100mL eggplant type bottle, rotation is steamed, except solvent obtains opaque viscous liquid,
It is eight hexamethylene alkylene oxide cage-type silsesquioxanes.Its nuclear magnetic resonance, NMR and infrared absorption analysis characterize data:29Si-NMR
(119MHz, CD3OD, 300K, ppm)-108.5；FTIR(cm-1, KBr) and 2967 (νasC-H), 2145 (νSi-H), 1097 (νSi-O-Si)
Embodiment 3:
1, eight hexamethylene alkylene oxide cage-type silsesquioxanes are prepared:
Preparation method is with embodiment 1；
2, silanization micron silica is prepared:
(1) micron silica is placed in 100 DEG C of vacuum drying ovens dry 24h；
(2) weigh dry powder body 10g to be placed in 500mL single port flask, be sequentially added into 100mL hexamethylene, 1.1mL γ-first
Base acryloxypropyl trimethoxy silane (γ-MPS), 0.51mL n-propylamine,
(3) after mixed liquor first ultrasonic 10min, then 30min is stirred at room temperature, then stirring reaction in 60 DEG C of oil bath pans
0.5h；
(4) reactant liquor is poured in rotary evaporating device vacuum rotary steam under conditions of 60 DEG C, will after solvent is distilled out of
Temperature is adjusted to 95 DEG C, and 45min is steamed in rotation further；
(5) finally the white powder of gained is placed in 80 DEG C of vacuum oven 18h, i.e. obtains the micron order of silanization
Silicon dioxide.
3, by weight 7:3 by sweet to bisphenol-A-glycidyl methacrylate (Bis-GMA) and dimethacrylate three
It is standby that alcohol ester (TEGDMA) mix homogeneously forms resin matrix；
4, measure 15.2g resin matrix in 50mL beaker, add 0.8g eight hexamethylene alkylene oxide cage-type silsesquioxane,
Stir, ultrasonic 0.5h；
5,0.4g camphorquinone (CQ), 0.4g (dimethylamino)-ethyl benzoate (EDAB), 0.4g hexafluoro iodic acid hexichol are added
Base iodine salt (PI), lucifuge stirs, the ultrasonic 2h of lucifuge；
6, adding 24g silanization micron silica, lucifuge adds in resin, and lucifuge stirs, and makes silanization micron dioxy
SiClx and the abundant moistening of resin；
7, after composite resin lucifuge being stirred, the ultrasonic 2h of lucifuge；
8, vacuum degassing bubble, pour into mould, blue light solidification 60s after i.e. can get composite resin material；
9, material is carried out polymerization shrinkage, mechanical property, the test of water suction solubility property.
Embodiment 4:
1, eight hexamethylene alkylene oxide cage-type silsesquioxanes are prepared:
Preparation method is with embodiment 1；
2, silanization micron silica is prepared:
Preparation method is with embodiment 3；
3, by weight 7:3 by sweet to bisphenol-A-glycidyl methacrylate (Bis-GMA) and dimethacrylate three
It is standby that alcohol ester (TEGDMA) mix homogeneously forms resin matrix；
4, measure 14.4g resin matrix in 50mL beaker, add 1.6g eight hexamethylene alkylene oxide cage-type silsesquioxane,
Stir, ultrasonic 0.5h；
5,0.4g camphorquinone (CQ), 0.4g (dimethylamino)-ethyl benzoate (EDAB), 0.4g hexafluoro iodic acid hexichol are added
Base iodine salt (PI), lucifuge stirs, the ultrasonic 2h of lucifuge；
6, adding 24g silanization micron silica, lucifuge adds in resin, and lucifuge stirs, and makes silanization micron dioxy
SiClx and the abundant moistening of resin；
7, after composite resin lucifuge being stirred, the ultrasonic 2h of lucifuge；
8, vacuum degassing bubble, pour into mould, blue light solidification 100s after i.e. can get composite resin material；
9, material is carried out polymerization shrinkage, mechanical property, the test of water suction solubility property.
Embodiment 5:
1, eight hexamethylene alkylene oxide cage-type silsesquioxanes are prepared:
Preparation method is with embodiment 1；
2, silanization micron silica is prepared:
Preparation method is with embodiment 3；
3, by weight 7:3 by sweet to bisphenol-A-glycidyl methacrylate (Bis-GMA) and dimethacrylate three
It is standby that alcohol ester (TEGDMA) mix homogeneously forms resin matrix；
4, measure 13.6g resin matrix in 50mL beaker, add 2.4g eight hexamethylene alkylene oxide cage-type silsesquioxane,
Stir, ultrasonic 0.5h；
5,0.4g camphorquinone (CQ), 0.4g (dimethylamino)-ethyl benzoate (EDAB), 0.4g hexafluoro iodic acid hexichol are added
Base iodine salt (PI), lucifuge stirs, the ultrasonic 2h of lucifuge；
6, adding 24g silanization micron silica, lucifuge adds in resin, and lucifuge stirs, and makes silanization micron dioxy
SiClx and the abundant moistening of resin；
7, after composite resin lucifuge being stirred, the ultrasonic 2h of lucifuge；
8, vacuum degassing bubble, pour into mould, blue light solidification 60s after i.e. can get composite resin material；
9, material is carried out polymerization shrinkage, mechanical property, the test of water suction solubility property.
Embodiment 6:
1, eight hexamethylene alkylene oxide cage-type silsesquioxanes are prepared:
Preparation method is with embodiment 1；
2, silanization micron silica is prepared:
Preparation method is with embodiment 3；
3, by weight 7:3 by sweet to bisphenol-A-glycidyl methacrylate (Bis-GMA) and dimethacrylate three
It is standby that alcohol ester (TEGDMA) mix homogeneously forms resin matrix；
4, measure 12.8g resin matrix in 50mL beaker, add 3.2g eight hexamethylene alkylene oxide cage-type silsesquioxane,
Stir, ultrasonic 0.5h；
5,0.4g camphorquinone (CQ), 0.4g (dimethylamino)-ethyl benzoate (EDAB), 0.4g hexafluoro iodic acid hexichol are added
Base iodine salt (PI), lucifuge stirs, the ultrasonic 2h of lucifuge；
6, adding 24g silanization micron silica, lucifuge adds in resin, and lucifuge stirs, and makes silanization micron dioxy
SiClx and the abundant moistening of resin；
7, after composite resin lucifuge being stirred, the ultrasonic 2h of lucifuge；
8, vacuum degassing bubble, pour into mould, blue light solidification 60s after i.e. can get composite resin material；
9, material is carried out polymerization shrinkage, mechanical property, the test of water suction solubility property.
Gear division composite resin material component and each constituent content (wt%)
| Component | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Bis-GMA | 24.5 | 23.1 | 21.7 | 20.3 |
| TEGDMA | 10.5 | 9.9 | 9.3 | 8.7 |
| POSS | 2 | 4 | 6 | 8 |
| CQ | 1 | 1 | 1 | 1 |
| EDAB | 1 | 1 | 1 | 1 |
| PI | 1 | 1 | 1 | 1 |
| SiO2 | 60 | 60 | 60 | 60 |
Gear division composite resin material cubical contraction (%)
| Component | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Cubical contraction (%) | 2.83 | 2.42 | 2.36 | 2.23 |
Gear division composite resin material flexural strength (MPa)
| Component | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Flexural strength (MPa) | 105.69 | 147.69 | 158.22 | 211.58 |
Gear division composite resin material compressive strength (MPa)
| Component | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Compressive strength (MPa) | 120.55 | 135.97 | 152.60 | 163.4 |
Gear division composite resin material shore hardness HD (%)
| Component | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Shore hardness HD | 88.2 | 90.1 | 91.3 | 90.0 |
Gear division composite resin material hygroscopicity value (μ g mm-3) and solubility value (μ g mm-3)
| Component | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Hygroscopicity value (μ g mm-3) | 1.15 | 1.04 | 0.12 | 0.11 |
| Solubility value (μ g mm-3) | 2.92 | 2.04 | 1.22 | 0.44 |
Claims (2)
1. an eight hexamethylene alkylene oxide cage-type silsesquioxane, its structural formula is as follows:
Eight hexamethylene alkylene oxide cage-type silsesquioxanes the most as claimed in claim 1, it is characterised in that use following steps to enter
Row preparation:
(1) in round-bottomed flask, add Tetramethylammonium hydroxide, methanol aqueous solution, stir in ice bath, be subsequently adding four ethoxies
Base silane, is stirred at room temperature 24h, i.e. obtains the eight poly-tetramethyl ammonium cage-type silsesquioxanes being scattered in solution；
(2) by this mixture under condition of ice bath, it is added dropwise to another and has added the three of normal hexane and dimethylchlorosilane
In mouth flask, this mixture is stirred at room temperature 3h；Use pear funnel separatory, take supernatant liquid rotation and steam, sucking filtration, cleans with methanol
3 times, obtain white powder solid, be dried, i.e. obtain eight poly-hydrogen-based dimethylsilyl cage-type silsesquioxanes；
(3) in there-necked flask, add dry toluene, take eight poly-hydrogen-based dimethylsilyl cage-type silsesquioxanes, stirring
5min, addition 1,2-epoxy 4-vinyl cyclohexane, add catalyst platinum (0)-1,3-divinyl-1,1,3,3-tetramethyl two
Silicone complex Pt；Stir at 50 DEG C, react 24h；Cooling, adds dry active charcoal, after stirring 5min；Mixture passes through
The poly tetrafluoroethylene of 0.45 μm, filters, vacuum rotary steam, obtains opaque viscous liquid, is eight hexamethylene alkylene oxide cage modles times
Half siloxanes.
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| CN107057517A (en) * | 2016-12-22 | 2017-08-18 | 广东通科技股份有限公司 | A kind of silicon nitrogen phosphorus cooperative flame retardant aqueous epoxy resins of silsesquioxane crosslinking and preparation method thereof |
| CN113583038A (en) * | 2021-07-27 | 2021-11-02 | 合盛硅业(鄯善)有限公司 | Octamethylcyclotetrasiloxane purification method |
| CN115991876A (en) * | 2023-03-23 | 2023-04-21 | 广东粤港澳大湾区黄埔材料研究院 | Composite rubber material and application thereof in new energy automobile tires |
| WO2023083325A1 (en) * | 2021-11-12 | 2023-05-19 | 北京深云智合科技有限公司 | Flame retardant and use thereof, and fire-resistant epoxy resin |
| CN116143990A (en) * | 2023-03-14 | 2023-05-23 | 温州东润新材料科技有限公司 | Organosilicon modified TPU composite material and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107057517A (en) * | 2016-12-22 | 2017-08-18 | 广东通科技股份有限公司 | A kind of silicon nitrogen phosphorus cooperative flame retardant aqueous epoxy resins of silsesquioxane crosslinking and preparation method thereof |
| CN113583038A (en) * | 2021-07-27 | 2021-11-02 | 合盛硅业(鄯善)有限公司 | Octamethylcyclotetrasiloxane purification method |
| WO2023083325A1 (en) * | 2021-11-12 | 2023-05-19 | 北京深云智合科技有限公司 | Flame retardant and use thereof, and fire-resistant epoxy resin |
| CN116143990A (en) * | 2023-03-14 | 2023-05-23 | 温州东润新材料科技有限公司 | Organosilicon modified TPU composite material and preparation method thereof |
| CN115991876A (en) * | 2023-03-23 | 2023-04-21 | 广东粤港澳大湾区黄埔材料研究院 | Composite rubber material and application thereof in new energy automobile tires |
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